Patent GB-346677-A (GB)
Title: Process for the manufacture and production of condensation products containing nitrogen
IPC: C09B6/00
Filed: 1929-10-08
Abstract: Anthraquinone vat dyes.-Vat dyes of the acridone series are made by condensing an ester or amide of an o-aminoanthraquinone carboxylic acid with a negatively substituted heterocyclic compound or with a negatively substituted isocyclic compound which contains a system of at least four condensed rings, such negatively substituted compounds having a free ortho position to the negative substituent, or an ester or amide of an anthraquinone carboxylic acid containing a negative substituent in o-position to the carboxylic group with a heterocyclic compound, or with an isocyclic compound having a system of at least four condensed rings, containing a nitrogen atom and a replaceable hydrogen atom attached thereto, and having a free o-position to the nitrogen atom, and effecting ring closure to form the corresponding acridone.  As negatively substituted and nitrogenous compounds, derivatives of benzanthrones, anthanthrones, dibenzanthrones, isodibenzanthrones, allo-ms-naphthodianthrones, dibenzpyrenequinones, ms-benzdianthrones, ms-naphthodianthrones, ms-anthradianthrones, pyranthrones, acridones, flavanthrones, benzanthronepyrazolanthrones, dipyrazolanthrones, and perylenequinones are specified.  The primary condensation with the esters or amides is preferably effected in the presence of solvents or diluents, such as naphthalene or nitrobenzene, acid-binding agents, and catalysts, such as copper or its compounds.  The products may be purified by known methods, such as by crystallization from sulphuric acid or organic solvents, or by treating with oxidizing agents, such as hypochlorites.  The conversion to the acridones is effected by known methods, such as by treatment with acid or alkaline condensing agents, including manganese dioxide and sulphuric acid, anhydrous metal chlorides, or acid chlorides such as phosphorus pentachloride.  In examples, (1) dibrom-3 : 4 : 8 : 9-dibenzpyrene-5 : 10-quinone (example 6 of Specification 327,756, [Class 2 (iii), Dyes &c.], is condensed with the methyl ester of 1-aminoanthraquinone-2-carboxylic acid (the product dyes cotton in red-violet shades) and ring-closed to the acridone (which dyes in red-brown shades) by heating with sulphuric acid; instead of the methyl ester, the ethyl or phenyl esters may be used, while the monobrom-3 : 4 : 8 : 9-dibenzpyrene 5 : 10-quinone (made by brominating in acid solution) yields products dyeing in brown shades, (2) 6-chlorbenzanthrone is condensed with 1-aminoanthraquinone-2-carboxylic acid methyl ester and the product treated with alcoholic potash to yield a dyestuff dyeing in violet-grey to black shades, (3) monoamino-allo-ms-naphthodianthrone (example 1 of Specification 339,659, [Class 2 (iii), Dyes &c.] is condensed with 1-chloranthraquinone-2-carboxylic acid ethyl ester and the product (which dyes in violet-grey shades) ring-closed to the acridone (dyeing in red-violet shades) by means of chlorsulphonic acid, (4) monoamino-ms-benzdianthrone (made by nitrating ms-benzdianthrone in nitrobenzene and reducing) is condensed with 1-chloranthraquinone-2-carboxylic acid ethyl ester and the product treated with sulphuric acid and manganese dioxide, or first with sulphuric acid and then with aluminium chloride, to yield a dyestuff dyeing in brown-green shades, and (5) the condensation product from 8-chlorbenzanthrone and 1-aminoanthraquinone-2-carboxylic acid methyl ester is treated with sulphuric acid; the product dyes fast brown shades. Specification 337,374, [Class 2 (iii), Dyes &c.], also is referred to.  The Provisional Specification describes the treatment of amino - (or negatively substituted) - anthraquinone carboxylic esters or amides in general with negatively substituted or nitrogenous compounds of the classes set out above, with or without further condensation to form acridones, and specifies negatively substituted or nitrogenous bodies of the indigo and thioindigo series, as well as halogen derivatives of condensation products of dicarboxylic anhydrides with o-diamines.  It also includes additional examples, in which (1) 1-aminoanthraquinone-2-carboxylic acid ethyl ester is condensed with (a) bromo-4 : 5 : 8 : 9-dibenzpyrene-3 : 10-quinone (example 2 of Specification 333,165, [Class 2 (iii), Dyes &c.] to give a dyestuff dyeing in violet shades, (b) dibromanthanthrone, made by brominating anthanthrone in 5 per cent oleum, to give a product dyeing in violet shades, (c) dibromallo-ms-naphthodianthrone (made by bromination in nitrobenzene according to Specification 303,184, [Class 2 (iii), Dyes &c.] to give a product dyeing in blue-grey shades, (d) 6 : 61-dibromisodibenzanthrone (reddish-blue), (e) 3:31-dibromflavanthrone (green), (f) 6-aminobenzanthrone, and (g) monoaminoanthanthrone (made by nitrating anthanthrone in nitrobenzene and reducing), (2) dibrom - 3 : 4 : 8 : 9-dibenzpyrene-5 : 10-quinone (above) is condensed with 2-aminoanthraquinone-3-carboxylic acid ethyl ester; the product is a brown powder, and (3) dibromanthanthrone (above) is condensed with 1 - aminoanthraquinone - 2 - carboxylic acid amide (or anilide, to give products dyeing in blue to violet shades.